Technical Abstract: Oxygen-containing carboxyl, hydroxyl, and phenolic surface functional groups of soil organic and mineral components play central roles in binding metal ions, and biochar amendment can provide means of increasing these surface ligands in soil. In this study, positive matrix factorization (PMF) was first employed to fingerprint the principal components responsible for the stabilization of heavy metals (Cu, Ni, Cd, Pb) and the release of selected elements (Na, Ca, K, Mg, S, Al, P, Zn) and the pH change in biochar amended soils. The PMF analysis indicated that effective heavy metal stabilization occurred concurrently with the release of Na, Ca, S, K, and Mg originating from soil and biochar, resulting in as much as an order or magnitude greater equilibrium concentrations relative to the soil-only control. In weathered acidic soil, the heavy metal (especially Pb and Cu) stabilization ability of biochar directly correlated with the amount of oxygen functional groups revealed by the O/C ratio, pHpzc, total acidity, and by the 1H NMR analysis. Equilibrium speciation calculation showed minor influence of hydrolysis on the total soluble metal concentration, further suggesting the importance of binding by surface ligands of biochar that is likely to be promoted by biochar-induced pH increase.